EP0600309B1 - Procédé de préparation continu de nitrites d'alkyle - Google Patents
Procédé de préparation continu de nitrites d'alkyle Download PDFInfo
- Publication number
- EP0600309B1 EP0600309B1 EP93118554A EP93118554A EP0600309B1 EP 0600309 B1 EP0600309 B1 EP 0600309B1 EP 93118554 A EP93118554 A EP 93118554A EP 93118554 A EP93118554 A EP 93118554A EP 0600309 B1 EP0600309 B1 EP 0600309B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- column
- process according
- nitrogen dioxide
- alcohol
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/04—Preparation of esters of nitrous acid
Definitions
- the present invention relates to a process for the preparation of alkyl nitrites from nitrogen dioxide and alcohols in a countercurrent column.
- Alkyl nitrites (alkyl esters of nitrous acid) are used in many different ways, for example as additives for motor oils, as stabilizers for unsaturated organic compounds, as spasmolytics, as reagents for oximation, nitrosation and diazotization as well as auxiliary substances for chemical synthesis.
- alkyl nitrites which is easy to carry out in the laboratory, is to react sodium nitrite with strong acids, for example with sulfuric acid, in the presence of the alcohol in question: 2 NaNO 2nd + 2 ROH + H 2nd SO 4th ⁇ 2 RONO + Na 2nd SO 4th + 2H 2nd O
- the process according to equation (1) is based on the high esterification rate of the nitrous acid with the alcohol, the reaction conditions being able to be chosen so that the alkyl nitrite formed can be removed from the reaction equilibrium in gaseous form, if appropriate by distillation.
- the disadvantages of this process lie in the use of expensive starting materials, such as sodium nitrite, and in the inevitable occurrence of large amounts of unusable inorganic salts, in particular sodium sulfate.
- alkyl nitrites Another method of producing alkyl nitrites is based on the use of nitrogen oxides. Nitrogen monoxide, oxygen and the alcohol in question are preferably reacted with one another, the following reactions taking place: 2 NO + O 2nd ⁇ 2 NO 2nd NO + NO 2nd ⁇ N 2nd O 3rd ROH + N 2nd O 3rd ⁇ RONO + ENT 2nd RAW + ENT 2nd ⁇ RONO + H 2nd O N 2nd O 3rd + H 2nd O ⁇ 2 ENT 2nd
- reaction equation (6) is generally unavoidable, since the dinitrogen trioxide formed according to reaction equation (3) can react not only with the alcohol in the sense of equation (4), but also with the water formed according to equation (5) . In the presence of sufficient, especially excess, amounts of alcohol, however, the nitrous acid formed is trapped in the sense of reaction equation (5) to form the desired alkyl nitrite and water and is therefore not lost as waste.
- EP 310 191 describes the formation of lower alkyl nitrites by the reaction of nitrogen monoxide, oxygen and the corresponding alcohols in a special apparatus containing a reaction and a rectification zone, the water obtained in the course of the alkyl nitrite production being continuously removed from the ascending product gas stream by washing becomes. Disadvantageous in this process, the use of the technically poorly available nitrogen monoxide is used.
- a process for the preparation of C 1 -C 6 alkyl nitrites by reacting nitrogen dioxide with C 1 -C 6 alcohols was found, which is characterized in that the column is operated in a countercurrent Alcohol or an alcohol / water mixture is fed into the upper part of the column and the nitrogen dioxide or a nitrogen dioxide / inert gas mixture is fed into the lower part of the column and the resulting alkyl nitrite is taken off as top product and the resulting nitric acid as bottom product from the column.
- Alcohols for the process according to the invention are straight-chain and branched C 1 -C 6 -alkanols, preferably straight-chain C 1 -C 4 -alkanols and particularly preferably methanol and ethanol. Methanol should be mentioned in particular.
- the molar ratio of the metered alcohol to the nitrogen dioxide fed in is 0.3 to 1: 1, preferably 0.4 to 0.8: 1 and particularly preferably 0.5 to 0.7: 1.
- the molar ratio of metered water to the nitrogen dioxide fed in is 0 to 2: 1, preferably 0.2 to 1.6: 1 and particularly preferably 0.8 to 1: 1.
- the lower limit zero in the general range indicates that the process according to the invention can be carried out without metered water.
- the non-zero lower limit in the preferred ranges indicates that the process according to the invention is preferably carried out in the presence of metered water.
- the pressure under which the process according to the invention is carried out is based, inter alia, on the material data and phase equilibria of the components involved, and also on economic considerations in the sense of achieving the maximum possible space-time yield and on the requirements of safety technology.
- a pressure procedure is advantageous.
- the process according to the invention can therefore be carried out both under normal pressure and under reduced or elevated pressure carry out.
- the pressure range is from 0.5 to 10, preferably 0.8 to 8, particularly preferably 1 to 5 bar.
- the nitrogen dioxide used according to the invention can be used as such or in the form of a mixture with inert gases.
- inert gases are, for example, nitrogen, carbon dioxide, argon, carbon monoxide, preferably nitrogen and carbon dioxide.
- Such an inert gas can be fed into the reactor separately or as a mixture with nitrogen dioxide.
- the volume ratio (Nl / Nl) of the inert gas to nitrogen dioxide is 0 to 5: 1, preferably 0.1 to 3: 1 and particularly preferably 0.2 to 2: 1.
- the lower limit zero of the volume ratio mentioned indicates that the process according to the invention can be carried out without the use of inert gases.
- the non-zero lower limit in the preferred ranges indicates that work is preferably carried out in the presence of such an inert gas.
- the use of larger amounts of inert gas, e.g. Inert gas: nitrogen dioxide> 2, in the process according to the invention is particularly advantageous in the production of higher alkyl nitrites.
- a reaction column which ensures a large phase interface (gaseous / liquid) and intimate mixing of the liquid and the gaseous phase.
- trays such as bubble-cap trays, perforated perforated trays, valve trays, slotted trays, etc., as are common for thermal separation, by packing of all kinds, as is customary in thermal separation operations, or by equipping the column with unordered packing of all kinds or with ordered packings of metal, ceramic, plastic, glass or other materials which are inert towards the reactants of the process according to the invention.
- Such columns with internals, fillings or packings and the fillings and packings themselves are commercially available and known to the person skilled in the art.
- Structured packings are preferably used.
- the load on the reaction apparatus based on the total amount of gas fed in (nitrogen dioxide and possibly inert gas) is 10 to 3000, preferably 20 to 2000 and particularly preferably 40 to 1000 Nl / l of free volume in the reaction column per hour. These conditions ensure a sufficient dwell time in order to achieve the most complete conversion possible.
- water is metered in when carrying out the process according to the invention, it can be used separately or in a mixture with the alcohol.
- the alcohol is preferably introduced into the column above the metered addition of water.
- the product stream with the desired alkyl nitrite is removed from the reaction column at the top in gaseous form.
- the alcohol contained therein can be at least partially removed therefrom by cooling and / or by compressing the product stream; the alcohol thus recovered can be returned to the reaction.
- the alkyl nitrite contained in the overhead stream which may be in a mixture with alcohol, can be at least partially removed from the latter by washing with a suitable washing medium, by vigorous cooling and / or by compressing the gaseous product stream; the remaining inert gas, if one was used, can be returned to the reaction.
- the alkyl nitrite produced according to the invention can be used directly for many other reactions, such as nitrosations, diazotizations, etc.
- this inert gas is obtained after the reactions mentioned and can be recycled therefrom into the process according to the invention.
- a carbon dioxide gas stream of 10 l / h was mixed with a nitrogen dioxide gas stream of 2.5 l / h (0.112 mol / h), heated to 25 ° C. and at the lower end of a tube filled with Raschig rings and heated to 25 ° C. initiated (dimensions: 1.6 cm diameter, 50 cm height).
- Example 2 The experiment described in Example 1 was repeated, the gas stream and the reaction tube being heated to 40 ° C. instead of 25 ° C. The gaseous overhead stream was analyzed. Result: Carbon dioxide 84% Methyl nitrite 10% Methanol 6%
- a carbon dioxide gas stream of 10 l / h was mixed with a nitrogen dioxide gas stream of 7.5 l / h (0.335 mol / h), heated to 25 ° C. and at the lower end of a tube filled with Raschig rings and heated to 25 ° C. initiated (dimensions: 1.6 cm diameter, 50 cm height).
- a carbon dioxide gas stream of 20 l / h was mixed with a nitrogen dioxide gas stream of 12.3 l / h (0.549 mol / h), heated to 25 ° C. and at the lower end of a tube filled with Raschig rings and heated to 25 ° C. initiated (dimensions: 1.6 cm diameter, 50 cm height).
- a carbon dioxide gas stream of 10 l / h was mixed with a nitrogen dioxide gas stream of 2.5 l / h (0.111 mol / h), heated to 25 ° C. and at the lower end of a tube filled with Raschig rings and heated to 25 ° C. initiated (dimensions: 1.6 cm diameter, 50 cm height).
- a carbon dioxide gas stream of 10 l / h was mixed with a nitrogen dioxide gas stream of 2.5 l / h (0.111 mol / h), heated to 30 ° C. and at the lower end of a tube filled with Raschig rings and heated to 30 ° C. initiated (dimensions: 1.6 cm diameter, 50 cm height).
- a carbon dioxide gas stream of 10 l / h was mixed with a nitrogen dioxide gas stream of 2.5 l / h (0.111 mol / h) and introduced into 200 ml of methanol at 25 ° C. with stirring.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Claims (10)
- Procédé de préparation de nitrites d'alkyle C1-C6 par réaction de dioxyde d'azote avec des alcools C1-C6, caractérisé en ce qu'on introduit dans une colonne fonctionnant à contre-courant l'alcool ou un mélange alcool/eau à la partie supérieure de la colonne et qu'on introduit le dioxyde d'azote ou un mélange dioxyde d'azote/gaz inerte dans la partie inférieure de la colonne et on prélève le nitrite d'alkyle formé comme produit de tête et l'acide nitrique coproduit comme produit de pied de la colonne.
- Procédé selon la revendication 1, caractérisé en ce qu'on utilise des alcools à chaîne droite C1-C4.
- Procédé selon la revendication 2, caractérisé en ce qu'on utilise du méthanol ou de l'éthanol.
- Procédé selon la revendication 1, caractérisé en ce que le rapport molaire de l'alcool au dioxyde d'azote est 0,3 à 1:1, de préférence de 0,4 à 0,8:1, surtout 0,5 à 0,7:1.
- Procédé selon la revendication 1, caractérisé en ce que le rapport molaire de l'eau au dioxyde d'azote est 0 à 2:1, de préférence 0,2 à 1,6:1, surtout 0,8 à 1:1.
- Procédé selon la revendication 1, caractérisé en ce qu'on travaille sous une pression de 0,5 à 10 bar, de préférence 0,8 à 8 bar, surtout 1 à 5 bar.
- Procédé selon la revendication 1, caractérisé en ce qu'on travaille à une température de 0 à 90°C, de préférence 10 à 80°C.
- Procédé selon la revendication 1, caractérisé en ce que le rapport volumique du gaz inerte au dioxyde d'azote, exprimé en Nl/Nl est de 0 à 5:1, de préférence 0,1 à 3:1, surtout 0,2 à 2:1.
- Procédé selon la revendication 1, caractérisé en ce que la charge de la colonne de réaction avec les gaz alimentés est de 10 à 3000, de préférence 20 à 2000, surtout à 40 à 1000 Nl/l de volume de colonne libre par heure.
- Procédé selon la revendication 1, caractérisé en ce qu'on introduit l'alcool après le dosage de l'eau dans la colonne.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4240311 | 1992-12-01 | ||
DE4240311A DE4240311A1 (de) | 1992-12-01 | 1992-12-01 | Verfahren zur kontinuierlichen Herstellung von Alkylnitriten |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0600309A1 EP0600309A1 (fr) | 1994-06-08 |
EP0600309B1 true EP0600309B1 (fr) | 1997-09-03 |
Family
ID=6474059
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93118554A Expired - Lifetime EP0600309B1 (fr) | 1992-12-01 | 1993-11-18 | Procédé de préparation continu de nitrites d'alkyle |
Country Status (5)
Country | Link |
---|---|
US (1) | US5412147A (fr) |
EP (1) | EP0600309B1 (fr) |
JP (1) | JP2931751B2 (fr) |
DE (2) | DE4240311A1 (fr) |
ES (1) | ES2108188T3 (fr) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG71167A1 (en) * | 1997-10-21 | 2000-03-21 | Ube Industries | Process for producing alkyl nitrite |
US7045152B2 (en) * | 1999-09-08 | 2006-05-16 | Duke University | Treating pulmonary disorders with gaseous agent causing repletion of GSNO |
US6314956B1 (en) | 1999-09-08 | 2001-11-13 | Duke University | Pulmonary delivery of NO group-containing compound in gas form to treat respiratory, cardiac and blood disorders |
US20040225275A1 (en) * | 2001-08-02 | 2004-11-11 | Reynolds James Dixon | Fetal physiology during maternal surgery or diagnosis |
US6676855B2 (en) * | 2001-08-02 | 2004-01-13 | Duke University | Use of a blood-flow decrease preventing agent in conjunction with insufflating gas |
EP2030964A1 (fr) * | 2007-08-06 | 2009-03-04 | Daicel Chemical Industries, Ltd. | Procédé de production d'esters de l'acide nitreux |
US20110003012A1 (en) * | 2007-09-10 | 2011-01-06 | Duke University | Treating patients with subarachnoid hemorrhage |
CN102219698B (zh) * | 2010-04-15 | 2014-04-23 | 中国石油化工股份有限公司 | 生产c1~c4烷基亚硝酸酯的方法 |
CN102276472B (zh) * | 2010-06-11 | 2013-12-04 | 中国石油化工股份有限公司 | 生产c1~c4烷基亚硝酸酯的方法 |
CN102924282B (zh) * | 2012-11-30 | 2014-03-12 | 西南化工研究设计院有限公司 | 一种生产亚硝酸烷基酯的工艺 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2739166A (en) * | 1950-12-19 | 1956-03-20 | John C Treacy | Process and resulting compositions |
US2831882A (en) * | 1955-09-16 | 1958-04-22 | Du Pont | Preparation of nitrite esters |
DE1156775B (de) * | 1961-10-04 | 1963-11-07 | Knapsack Ag | Verfahren zur kontinuierlichen Herstellung von Estern der salpetrigen Saeure |
US4353843A (en) * | 1981-01-23 | 1982-10-12 | Union Carbide Corporation | Preparation of nitrite esters |
US4908466A (en) * | 1987-09-29 | 1990-03-13 | Union Carbide Chemicals And Plastics Company Inc. | Process and reaction vessel for production of alkyl nitrite |
-
1992
- 1992-12-01 DE DE4240311A patent/DE4240311A1/de not_active Withdrawn
-
1993
- 1993-11-18 ES ES93118554T patent/ES2108188T3/es not_active Expired - Lifetime
- 1993-11-18 EP EP93118554A patent/EP0600309B1/fr not_active Expired - Lifetime
- 1993-11-18 DE DE59307262T patent/DE59307262D1/de not_active Expired - Fee Related
- 1993-11-24 US US08/157,779 patent/US5412147A/en not_active Expired - Fee Related
- 1993-11-25 JP JP5317454A patent/JP2931751B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0600309A1 (fr) | 1994-06-08 |
DE59307262D1 (de) | 1997-10-09 |
JP2931751B2 (ja) | 1999-08-09 |
JPH06199741A (ja) | 1994-07-19 |
ES2108188T3 (es) | 1997-12-16 |
DE4240311A1 (de) | 1994-06-09 |
US5412147A (en) | 1995-05-02 |
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